Adducts of hydroxyalkyl alkylene polyamines and acrylates



United States Patent 3,337,609 ADDUCTS 0F HYDROXYALKYL ALKYLENE POLYAMINES AND ACRYLATES Frank L. Williamson, South Plainfield, and Anthony R.

Olivo, South Somerville, N.J., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Feb. 3, 1966, Ser. No. 524,825 1 Claim. (Cl. 260-482) This application is a continuation-in-part of application Ser. No. 62,535, filed Oct. 14, 1960, now US. Patent No. 3,256,239.

This invention relates to adducts of hydroxyalkyl alkylene polyamines and acrylates. More specifically, this invention relates to adducts of hydroxyalkyl alkylene polyamines and acrylates which, when admixed with polyepoxides provide compositions which are particularly suitable as barrier coatings for thermoplastic containers such as polyethylene squeeze bottles preventing egress therefrom of packaged fluids and their vapors.

Polyethylene containers, which are otherwise desirable because of their flexibility over a wide range of temperatures, their relatively light weight, and their chemical inertness toward aqueous and non-aqueous fluids, have not found wide use in the packaging of liquid cosmetics and liquid organic chemicals due to the permeability shown by polyethylene to these liquids. The permeability of polyethylene to liquid cosmetics such as perfumes which contain essential oils and flavor components, illustrative of which are citrus oils, clove oils, orange oils, lemon oils, eugenol, isoeugenol and inonones, and also the permeability to organic liquids such as gasoline, toluene, ethyl alcohol, and ethyl acetate has seriously limited the use of polyethylene containers as packaging means for such liquids.

It has been found that when perfumes or organic liquids, as described, are packaged in polyethylene containers, the more volatile components of these liquids pass through the walls of the containers. Consequently, the packages undergo a loss of weight. In addition, the packaged liquids undergo a basic change in character due to the escape of their more volatile components. The escape of liquids from the tightly capped containers results in a greater pressure acting on the exterior of the containers than on the interior walls thereof as air cannot readily pass into the containers to replace the escaped liquids. This pressure differential often results in the distortion or collapsing of the Walls of the containers.

The problem of permeability of polyethylene has been attacked by various methods, none of which has resulted in an adequate solution. For example, it has been proposed to coat polyethylene surfaces with a variety of resinous coating compositions. Illustrative of one such composition is a copolymer of vinyl chloride and vinylidene chloride marketed under the trade name Saran. Saran has the following physical properties: specific gravity 1:65 to 1.72, tensile strength 20,000 to 40,000 lbs/square inch, impact strength 0.3 to 1.0 ft.-lb./notch inch, index of refraction 1.61, and dielectric strength 350 volts/mil.

Saran and other compositions which have been formulated and used as barrier coatings on polyethylene surfaces in order to improve the impermeability characteristics of polyethylene have not been found satisfactory in that they do not have good barrier action and, in addition, their adhesion to polyethylene surfaces is poor.

Polyethylene does not contain highly polar groups which could set up a strong electrostatic bond between the atoms of the coating composition and the polyethylene surfaces. Adhesion of resinous coating compositions to polyethylene surfaces depends upon mechanical factors, that is, the presence of rough, porous areas on the polyethylene surfaces into which the coatings can penetrate to form teeth or anchors. With coating or barrier compositions presently formulated, not only has the mechanical adhesion been weak but the coatings have not possessed an adequate degree of flexibility which would allow use of such compositions as coatings on surfaces of polyethylene squeeze bottles and flexible films.

It is an object of this invention to provide for adducts which, when added to polyepoxides, provide compositions suitable for use as a barrier coating for polyethylene surfaces.

The acrylates which are reacted with the hydroxyalkyl alkylene polyamines to produce the adducts of this invention have the general formula:

wherein: R is an alkyl radical preferably containing from 1 to 18 carbon atoms inclusive; R is either hydrogen or alkyl and when alkyl preferably containing a maximum of 2 carbon atoms; and the adduct itself contains an average of more than 2 amino-hydrogen atoms per molecule, preferably at least 3 amino-hydrogen atoms per molecule.

Illustrative of acrylates having the general formula previously given which can be reacted with hydroxyalkyl alkylene polyamines to produce the organic amine-acrylate adducts are the following: methylacrylate, ethylacrylate, n-propylacrylate, isopr-opylacrylate, n-butylacrylate, n-amylacrylatc, n-hexylacrylate, 2-ethylhexylacrylate, noctylacrylate, n-nonylacrylate,-n-laurylacrylate, pentadecylacrylate, octadecylacrylate, methylmethacrylate, methylethacrylate, isopropylmethacrylate, n-hexylmethacrylate, n-nonylmethacrylate, ethylethacrylate, n-propylethacrylate, n-butylethacrylate, n-amylethacrylate, n-hexylethacrylat-e, n'heptadecylacrylate, n-octadecyiethacrylate and the like. Specific hydroxyalkyl alkylene polyamines suitable for purposes of this invention are the hydroxyalkyl alkylene polyamines having the general formula:

wherein x is an integer from zero to 3 inclusive, n is an integer from 2 to 6 inclusive, R in each instance is a monovalent substituent being either hydrogen or a hydroxyalkyl group wherein the alkyl group preferably contains from 1 to 4 carbon atoms: inclusive, as for.

N-hydroxyethyl ethylene diamine NH CH CH NHCH CH OH N-hydroxyethyl pen-tamethylene diamine NH CH NHCH CH OH N-hydroxypr0py1 tetramethylene diamine NH (CH NHC H OH *N-hydroxyethyl diethylene triamlne NH C H NHC H NHC H OH 3 N,N-dihydroxyethyl diethylene triamlne NH C H NHC H N C H OH 2 N,N-dihydroxyethyl diethylene triamine NH C H NHC H OH 2 N-hydroxypropyl diethylene triamine NH C H NHC H NHC H OH N,N-dihydroxypropyl diethylene triamine NH C H NHC H N C H OH 2 N,N"-dihydroxypropyl diethylene triamine NH (C H NHC H OH) 2 N-hydroxyethyl propylene diamine NH CH CH CH NHCH CH OH N-hydroxypropyl propylene diamine NH C H NHC H OH N-hydroxyethyl dipropylene triamine NH C H NHC H NHC H OH N,Ndihydroxyethyl dipropylene 'triamine NH C H NHC H N C H OH 2 N,N-dihydrxyetl1y1 dipropylene triamine C2H4OII NHQCQHGN CaHsNHCzI'LOH Tris-hydroxyethyl triethylene tetramine (HOC H N (C H NH) C H OH Preparation of hydroxyalkyl alkylene polyamines is described in US. Patent 2,901,461 to V. Auerbach et al., issued Aug. 25, 1959.

The preparation of the organic amine-acrylate a-dducts can be conveniently accomplished by admixing, at temperatures greater than 0' C., the desired organic amine and acrylate. For example, when reacting a hydroxyalkyl alkylene polyamine containing at least 4 amino-hydrogen atoms, with an acrylate, it is customary to heat a mixture containing equimolar amounts of the reactants at a temperature of about 70 C. to about 150 C. to produce the organic amine-acrylate adduct. This react-ion can be represented by the equation which follows wherein, as can be seen, the amine preferentially adds across the olefinic double bond of the acrylate.

HOCHzCH NHC ThNHC HrNH CHz:CHC-=O O C H N-hydroxyethyldiethylene triamine ethylacrylate i H O-CHzGHg-NH C gH ANH Cfl-h-N-CH -C I-I C =0 N-hydroxyethyldiethylene triamine ethylaerylate When using an organic amine containing only 3 aminohydrogen atoms per molecule, it is then customary to react a mixture containing at least 2 moles of organic amine per mole of acrylate in order to obtain an adduct containing an average of more than 2 amino-hydrogen atoms per molecule. In that event the reaction will proceed in a manner described in the preceding paragraph.

For purposes of this invention, the organic amineacrylate adduct must contain an average of more than two amino-hydrogen atoms per molecule, preferably at least three amino-hydrogen atoms per molecule in order to provide an adduct which will cure polyepoxides to a hard, tough infusible state. Generally the number of moles of acrylate per mole of amine used will have a value of at least 0.5 and a maximum value equal to or less than the number of amino-hydrogen atoms of the amine minus two. It is obvious that mixtures of primary, secondary and tertiary amines will be produced when the acrylates are reacted with the organic amines. Mainly, however, the reaction between the organic amine and acrylate is one wherein the primary amino group or groups of the amine, being more reactive, will preferentially react with the acrylate.

The polyepoxides which can be cured with the amine acrylate adducts are those organic compounds having an epoxy equivalency of greater than one, that is, compounds having an average of more than one epoxy group, i.e.,

per molecule. These compounds, wherein the oxygen of the epoxy group is attached to vicinal carbon atoms, can be saturated or unsaturated, aliphatic, cycloaliphatic or heterocyclic, and can be substituted, with substituents such as halogen atoms, alkyl groups, ether groups and the like.

In further explanation of the term epoxy equivalency as used in this specification, it refers to the average number of epoxy groups contained in the average polyepoxide molecule. This value is obtained by dividing the molecular weight of the polyepoxide by its calculated epoxide equivalent weight. The epoxide equivalent weight is determined by heating a one gram sample of the polyepoxide with an excess of pyridinium chloride which is dissolved in pyridine. The excess pyridinium chloride is then back titrated with 0.1 N sodium hydroxide to an end point using phenolphthalein as the indicator. The epoxide equivalent weight is calculated by considering that one HCl molecule is equivalent to one epoxide group. If the polyepoxide is a single compound and all of its epoxy groups are intact, the epoxy equivalency values will be integers of whole numbers, such as 2, 3, 4 and the like. In those instances wherein the polyepoxide is a mixture of polyepoxides or contains some monomeric monoepoxides or where the polyepoxide has some of its epoxy groups hydrated or otherwise reacted, the epoxy equivalency values may contain fractions, such as 1.2, 1.5, 2.8 and the like.

Illustrative of polyepoxides which can be cured with the amine-acrylate adducts are the polyglycidyl ethers of polyhydric phenols, exemplified by the polyglycidyl ethers of such phenols as the mononuclear polyhydric phenols, resorcinol and pyrogallo, the dior polynuclear phenols, such as the bisphenols described in Bender et al., US. Patent 2,506,486, and polyphenylols such as the novolak condensation products of a phenol and a saturated or unsaturated aldehyde, containing an average of from 3 to 20 or more phenylol groups per molecule (cf. Phenoplasts, by T. S. Carswell, published in 1947 by Interscience Publishers, New York). Exemplary of suitable polyphenylols derived from a phenol and an unsaturated aldehyde such as acrolein are the triphenylols, pentaphenylols, and heptaphenylols described in US. Patent 2,885,385 to A. G. Farnham. The phenols may contain substituents such as alkyl, aryl or halogen ring substituents as exemplified by the alkyl resorcinols, tribromoresorcinol and the diphenols containing alkyl and halogen substituents on the aromatic ring (Bender et al., US. Patent 2,506,486). The polyhydric polynuclear phenols can consist of two or more phenols connected by such groups as methylene, alkylene or sulfone. The connecting groups are further exemplified by bis(phydroxyphenyl)methane, 2,2 bis-(p-hydroxyphenyDpropane and dihydroxydiphenyl sulfone.

Process for the preparation of polyglycidyl ethers of polyhydric phenols is described in detail in the Bender et al. patent (supra) and US. Patent 2,801,989 to A. G. Farnham.

Particularly desirable for purposes of this invention are the polyglycidyl ethers of the his(hydroxyphenyl) alkanes, as for example, the diglycidyl ether of 2,2'bis (p-hydroxyphenyl)propane and the diglycidyl ether of bis(p-hydroxyphenyDmethane. Other suitable polyglycidyl ethers of polyhydric phenols are enumerated in US. Patent 2,633,458 to E. C. Shokal.

Also suitable are the polyglycidyl ethers of polyhydric alcohols, such as the reaction products of epichlorohydrin and aliphatic compounds containing from two to four alcoholic hydroxyl groups, such as ethylene glycol, propane diols, butane diols, glycerine, hexane triols and the like. (Methods of preparing polyglycidyl ethers to polyhydric alcohols are described in US. Patent 2,898,349 to P. Zuppinger et a1.)

Other suitable polyglycidyl compounds are the polyglycidyl esters of polycarboxylic acids, such as the polyglycidyl esters of adipic acid, phthalic acid and the like.

Polyglycidyl esters of polycarboxylic acids are described in detail in U.S. Patent 2,870,170 to Payne et al. Also suitable are polyglycidyl compounds produced by reacting epichlorohydrin with aromatic amines, such as aniline, 2, 6-dimethyl aniline, p-toluidine, m-chloroaniline, p-aminodiphenyl, m-phenylene diamine, p-phenylene diamine, 4, 4'-diaminodiphenyl methane, or with amino phenols such as p-amino phenol, -amino-1-nnaphthol, 4-amino resorcinol, 2 methyl-4-amino phenol, 2-chloro-4-amino phenol and the like. Specific compounds include, among others, N,N-diglycidyl aniline, N,N-diglycidyl-2,6-dimethyl aniline, N,N,N',N'-tetraglycidyl-4,4-diamino diphenyl methane, the triglycidyl derivative of p-amino phenol wherein the amino-hydrogen and OH hydrogen atoms are replaced by glycidyl groups. Polyglycidyl derivatives of aromatic amines and amino phenols and methods for their preparation are further described in U.S. Patents 2,951,- 825 and 2,951,822 to N. H. Reinking et al. and N. H. Reinking. The so-called peracetic acid epoxides which are obtained by epoxidation across a double bond using peracetic acid, such as bis(2,3-epoxycyclopentyl)ether and the like are also suitable.

It is to be understood that all patents and literature references referred to in this specification are incorporated herein by reference.

Various amounts of the organic amine-acrylate adducts can be used to cure the polyepoxides to hard, tough, inful'ble products. Generally the organic amine-acrylate adducts are used in amounts such as to provide from about 0.2 to about 5 amino-hydrogen atoms per epoxy group, preferably in amounts so as to provide from about 0.5 to about 1.5 amino-hydrogen atoms per epoxy group. For optimum results, however, the organic amine acrylate adducts are used in stoichiometric amounts. For purposes of stoichiometric calculations, one epoxy group:

is deemed to react with one amino-hydrogen atom. The

actual amount of organic amine acrylate adduct used will depend upon the desired end properties of the resultant cured polyepoxide composition. For example, increasing the amount of adduct used, tends to increase the flexibility of the cured composition.

The polyepoxide and the organic amine acrylate adducts are combined by simply admixing the two together, generally at room temperature.

In those instances wherein the polyepoxide is a relatively low viscosity liquid, it is admixed directly with the adduct. Polyepoxides which are to viscous for ready mixing with the adducts can be heated to reduce their viscosity or liquid solvents can be added thereto in order to provide the desired fluidity. Normally solid polyepoxides are either melted or mixed with liquid solvents.

Suitable solvents for imparting the desired fluidity to such as acetone, methyl isobutyl ketone, isophorone and the like; esters, such as ethyl acetate, butyl acetate, ethylene glycol monoacetate, acetate of ethylene glycol monomethyl ether, and the like; alcohols, such as the methyl, ethyl and butyl ether of ethylene glycol or of diethylene glycol; chlorinated hydrocarbons such as trichloropropane, chloroform and the like. Also suitable in admixture with the solvents noted are the aromatic hydrocarbons, such as benzene, toluene, xylene and the like; alcohols, such as ethyl alcohol, isopropyl alcohol, n-butyl alcohol and the like. The actual amount of solvent used will depend upon the polyepoxide being employed. If desired, rather then using solvents of the type described, or in addition thereto, reactive liquid diluents containing a single epoxy group:

can be used in order to achieve the desired fluidity in the polyepoxide. Among suitable reactive liquid diluents are butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether and the like. In determining stoichiometric amounts with respect to the adducts, the presence of reactive diluents is taken into account.

Additional materials, such as fillers, pigments, fibers, dyes, plasticizers, peroxides such as benzoyl peroxide, accelerators such as triphenyl phosphite and the like can be added either to the polyepoxides or to the adducts, if desired.

In order to cure the polyepoxide compositions to hard, tough, infusible products, it is customary to heat the compositions at elevated temperatures, generally on the order to about C. to about 100 C. for a period of time ranging from about 1 to 3 hours. The actual heating cycle will depend upon the composition being cured. Room temperatures curing, about 25 C. can be effected but generally this takes a number of days.

These compositions, when they are to be used to formulate coating compositions, are prepared by admixing the desired polyepoxide and organic amine acrylate adduct in a suitable solvent, as for example, 2-ethoxyethanol or a mixture of methyl isobutyl ketone, toluene and butanol and then adjusting the' solids content of the solution to the desired value. Generally the solids content is from about 70 to about percent by weight. It is to be understood, however, that the actual solids content will depend upon the type of application technique used to i apply the coating solution. The compositions of this invention can be applied as coatings by such techniques as spraying, slushing, immersing, roller coating and by various other methods employed in the coating art.

Although the above compositions have been described as particularly useful for use as coatings, they also have wide utility in the preparation of molded articles, as for example, electrical castings, and can be used to encapsulate electrical components. In addition the adducts of this invention can be utilized as catalysts in the preparation of phenol-formaldehyde one and two step resins, corrosion inhibitors, in water systems, for ferrous metals, and as intermediates in the preparation of quaternary amines which find use as wetting agents and also as germicidal agents.

The-examples which follow are intended to further illustrate the present invention without limiting the scope thereof in any manner.

EXAMPLE I A. Preparation of the organic amine-acrylate adduct Into a. triple-necked flask, equipped with a stirrer and thermometer, there was added 2000 grams of 2-ethylhexylacrylate and 1400 grams of N-hydroxyethyldiethylenetriarnine. The resultant mixture was heated, with stirring, until the temperature of the contents of the flask reached 167 C. Heating was discontinued and the liquid, amine acrylate adduct in the flask was cooled to room temperature, about 25 C. The liquid, amine acrylate adduct was recovered and found to have a nitrogen assay, as determined by the Kjeldahl test, of 21.43 percent and an amino nitrogen equivalent of 160.5 grams per gram mole. Amino nitrogen equivalent was determined by titrating a sample of the adduct, in glacial acetic acid, with perchloric acid to a methyl violet end point and calculated using the equation:

Amino-nitrogen equivalent:

weight of sample (ml. of acid) (normality of acid) B. Preparation of a curable composition of diglycl'dyl ether of 2,2-bis(p-hydroxyphenyl)propane and the adduct of 1A 65 grams of the adduct of 1-A were thoroughly admixed at room temperature about 25 C., with 100 grams of diglycidyl ether of 2,2-bis(p-hydroxyphenyl)propane having an epoxide equivalent weight of 192. The composition was cast into bars having the following dimensions: inch thick, inch wide, 8 inches long. The bars were allowed to stand at room temperature, about 25 C., for 2 hours, were thereafter heated for two hours at 150 C., and then subjected to various tests which are noted below, along with the results of the tests.

Tensile strength (ASTM D638-52T) 2580 p.s.i. Tensile elongation (ASTM D638-52T) 0.06 Izod impact (ASTM D256-47T) 1.44 ft.-lbs./

inch notch.

Rockwell hardness (M-scale) 68.

EXAMPLE II Five four-ounce Boston Round bottles, produced from polyethylene having a density of 0.96, having a wall thickness of about 40 mils and previously treated with a solution of potassium dichromate solution in sulfuric acid, commonly referred to as a chromic acid treatment (the chromic acid treatment is described in detail in United States Patent to P. V. Horton, No. 2,668,- 134, issued Feb. 2, 1954) were slush coated with a coating composition having the following formulation.

Formulation: Amount, grns. Diglycidyl ether of 2,2-bis(p-hydroxyphenyl) propane having an epoxide equivalent weight Adduct of N-hydroxyethyldiethylenetriamine and Z-ethylhexylacrylate 55 Mixture of methyl isobutyl ketone, toluene and butanol 67 The slush coating of each bottle was accomplished as follows: each bottle was filled with the coating composition described above. Each bottle was then inverted and allowed to drain until the drops of the coating solution fell at the rate of about one drop every ten seconds. Thereafter each bottle was placed on its side and the solvent vapors removed through a suction tube inserted about A of the way inside the bottle. After about minutes of drying in this fashion, the suction tube was removed and the bottles air dried for 1 hour at room temperature, about C., and then heated for 1 hour at a temperature of 107 C. with the result that the coating compositions in each bottle cured to an infusible state. Coatings on each bottle were on the order of about 0.5 mil thick and each bottle weighed, on the average of 4.255 grams.

Each bottle was then filled with 100 cc. gasoline and 15 cc. water. The bottles were capped and stored in an atmosphere which was at 70 F. and a relative humidity of 50 percent, for varying periods of time. The percent weight loss after the storage time indicated is noted below.

Percent 'wt. loss Time: (av. of 5 bottles) 1 week 0.038

2 weeks 0.080

3 weeks 0.122

4 weeks 0.176

2 months 0.371

3 months 0.570

EXAMPLE III Two coating compositions were prepared using the diglycidyl ether, the amine acrylate adduct and the solvent described in Example II. Formulation of these coating compositions is noted below.

Formulation A: Amount, gms. Diglycidyl ether of 2,2-bis(p hydroxyphenyl) propane Amine acrylate adduct 2.75 Mixture of methylisobutylketone, toluene and butanol 19.5

Formulation B:

Diglycidyl ether of 2,2-bis(p-hydroxyphenyl) propane Amine acrylate adduct 27.5

Mixture of methylisobutylketone, toluene and butanol 8.5

Five four-ounce Boston Round polyethylene bottles were coated with Formulation A and the coatings cured, both operations conducted in a manner described in Example II. Five other four-ounce Boston Round polyethylene bottles were coated with Formulation B and the coatings cured, both operations conducted in a manner described in Example II. The polyethylene bottles used in conducting this example, produced from polyethylene having a density of 0.96, had a wall thickness of about 40 mils and were chromic acid treated.

The average weight of bottles coated with Formulation A was 4.563 grams.

The average weight of bottles coated with Formulation B was 4.751 grams.

Each bottle was then filled with cc. of gasoline and 15 cc. of water. The bottles were capped and stored in an atomosphere at 70 F. and a relative humidity of 50 percent, for varying periods of time. The percent weight loss after the storage time indicated is noted below. Bottles coated with Formulation A are identified as A; bottles coated with Formulation B are identified as B.

Percent wt. loss Time: (av. of 5 bottles) 1 week 0.010-A, 0.014B 2 weeks 0.020-A, 0.025B 3 weeks 0.024-A, 0.043B 4 weeks 0.033-A, 0.063B 2 months 0.070-A, 0.150B 3 months 0.109A, 0.245-B 4 months 0.151-A, 0.340B

For purposes of comparison, 30 bottles of the same kind as that described in Example III and also chromic acid treated were coated with a composition of diglycidyl ether of 2,2-bis(p-hydroxyphenyl)propane having an epoxide equivalent weight of 192 and a stoichoimetric amount of diethylene triamine. Each coating was applied and cured as described in Example III. Each coated bottle was filled with 100 cc. of gasoline and 15 cc. of water, capped and then stored in an atmosphere which was at 70 F. and a relative humidity of 50 percent. After 1 week the weight loss was 0.614 percent based on the average of the 30 coated bottles.

The results of the aforegoing examples clearly indicate that the adducts of this invention when added to polyepoxides provide compositions which when coated onto and cured on polyethylene surfaces provide coatings which substantially prevent passage of organic liquids through the polyethylene without in any way affecting the otherwise desirable properties of polyethylene, such as flexibility, toughness and inertness toward aqueous and nonaqucous fluids. In addition, these compositions, when applied as coatings and cured, not only exhibit excellent adhesive properties toward both untreated and treated polyethylene, i.e., polyethylene which has been subjected to chemical and/or electrical treatment in order to render it more receptive to coatings, but also possess a high degree of flexibility. These compositions, therefore, are particularly desirable as coatings for flexible polyethylene squeeze bottles and for flexible polyethylene films. Furthermore, cured products of the compositions retain both their excellent adhesion and flexibility characteristics over a wide range of temperatures and also on prolonged contact with the liquid which is packaged.

What is claimed is:

A reaction product of a hydroxyalkyl alkylene polyamine having the general formula:

wherein x has a value of 0 to 3 inclusive, n has a value of 2 to 6 inclusive and each R is selected from the group consisting of hydrogen and hydroxyalkyl wherein the alkyl group of hydroxyalkyl contains from one to four carbon atoms inclusive, the number of instances where R is a hydroxyalkyl group being at least one but less than x+2 and an acrylate having the general formula:

wherein R is selected from the group consisting of hydrogen and an alkyl group containing a maximum of 2 carbon atoms and R is an alkyl radical containing a maximum of 18 carbon atoms, said reaction product containing an average of more than two amino-hydrogen atoms per molecule, formed on reacting a mixture containing said amine and said acrylate wherein the number of moles of acrylate, per mole of amine, is about 0.5 to a maximum value of about the number of amino-hydrogen atoms of the amine minus two.

References Cited UNITED STATES PATENTS 2,824,851 2/1958 Hall 260-47 2,870,117 1/1959 Vogel et al 117-132 2,883,308 4/1959 Yamada et al 117-132 2,901,461 8/1959 Auerbach et al 260-47 LORRAINE A. WEINBERGER, Primary Examiner. ALBERT P. HALLUIN, Assistant Examiner. 

